Desiccant tablets for gas drying

ABSTRACT

Desiccant tablets including solid potassium formate are used to dry gas, especially in natural gas transmission lines. Preferred tablets comprise 1-4% potassium formate (most preferably 2-3%), up to 1% of a surfactant as a lubricant, and the balance desiccant salts, preferably calcium chloride.

RELATED APPLICATION

[0001] This application is a continuation-in-part of my application of the same title filed Mar. 9, 2001, Ser. No. 09/803,072, which is based upon and incorporates the entire disclosure and claims of my Provisional Application Serial No. 60/217,805 filed Jul. 12, 2000.

TECHNICAL FIELD

[0002] Tablets containing potassium formate are useful for drying gases because of their deliquescent properties.

BACKGROUND OF THE INVENTION

[0003] In the past, desiccants have been commonly used to dry gases such as natural gas, particularly for its transmission through pipelines. Typically the pipelines carry natural gas over hundreds of miles, and it is necessary and desirable to remove whatever moisture is present in the gas and/or in the pipeline. To this end, the art has employed common desiccant salts such as calcium chloride, made into tablets which tend to absorb the moisture.

[0004] An early patent to Hutchinson, U.S. Pat. No. 2,804,940, suggests passing a partially dehydrated natural gas upwards through a bed of solid particulate deliquescent material such as calcium, magnesium, or lithium chloride, or mixtures of them. Certain molar ratios of chlorides and bromides are suggested by Heath in U.S. Pat. No. 2,143,008 and by Thomas in U.S. Pat. No. 5,733,841; see also Thomas U.S. Pat. No. 5,766,309. for a good illustration of the placement of the solid deliquescent materials in a contemporary drying vessel; this patent (U.S. Pat. No. 5,766,309) is incorporated by reference herein in its entirety.

[0005] A solution of 40-70% potassium formate is suggested for use as a moisture absorbent in dehumidifiers and similar devices by Atkinson in U.S. Pat. No. 5,846,450.

SUMMARY OF THE INVENTION

[0006] Tablets are made of powdered or crystalline potassium formate and used to remove moisture from gases such as natural gas. The tablets may contain from 0.5% to 100% by weight potassium formate, the balance being alkali or alkaline earth metal formates (preferably sodium, calcium, cesium and/or magnesium formate), chlorides and/or bromides (preferably calcium chloride, potassium chloride, cesium chloride, lithium chloride, or mixtures thereof). The tablet is preferably made under compression and, for use in gas dryers in natural gas transmission lines, preferably weighs about 7 to 15 grams so it can conveniently form a bed in a more or less conventional gas dryer. A pillow shape is convenient, but no particular shape is required for this invention. Preferred tablets comprise 97.5% calcium chloride and 2.5% potassium formate. An additional 0.5% of a binder, which is preferably sodium lauryl sulfonate, may also be used. The preferred tablets need not use these exact proportions, however—they may comprise 0.5% to 100% potassium formate, an additional 0.01% by weight to 1% by weight of a surfactant used as a lubricant, and the balance one or more alkali metal or alkaline earth metal halides.

[0007] Tablets made as described above and containing 1-4% potassium formate, most preferably 2-3% potassium formate, are particularly advantageous not only for their gas drying abilities but also because recrystallization in the sump is minimal or nonexistent.

DETAILED DESCRIPTION OF THE INVENTION

[0008] Comparisons have been made of the tablets of the present invention, containing potassium formate, to various tablets containing calcium chloride. For the comparisons, tablets were made of each of the materials indicated. Tablets of each description were placed in a screen basket which in turn was placed in a humidifier and permitted to remove moisture from the same air. The baskets retained the tablets but permitted liquid to drain into a pan. The pans were preweighed and weighed again periodically. Results are reported in terms of weight gain (liquid) in the pans, in grams, over time. Table I presents the data obtained.

[0009] In Table 1 and elsewhere herein, CaCl2 77% is calcium chloride containing 23% moisture. 10%KCOOH means 77%CaCl₂ having an additional (based on the calcium chloride) 10% potassium formate. “94%+10%KF” means, in flake form, 94% calcium chloride, 6% moisture and an additional 10% potassium formate based on the calcium chloride and moisture. TABLE 1 Weight increase over time (grams) Product 3 hours 18 hours 25 hours 90 hours CaCl2 77% 0.7295 4.609  6.5831 19.5703 CaCl2 77% 0.4096 3.2685 4.5123 17.9454 +10% KCOOH 0.6026 6.0434 7.6411 19.6084 +10% KCOOH 0.781  5.8817 7.7085 22.1131 94% + 10% KF 0.002  4.5483 5.6003 16.0585 94% + 10% KF 0.0931 3.2718 4.294  16.8932

[0010] TABLE 2 Weight increase over time (grams) Product 16 hours 20 hours 24 hours 40 hours CaCl2 77% 8.9011 9.6635 10.0889  12.4836 94% + 2.5% KF 6.9944 8.4999 9.5212 14.1517 94% + 5.0% KF 8.245  9.0611 9.6312 12.8922 94% + 7.5% KF 7.8536 8.7734 9.9184 13.9462 94% + 10% KF 7.259  8.1575 9.1607 13.2313

[0011] In Table 2, “94%+10%KF” means 94% calcium chloride, 6% moisture and an additional 10% potassium formate based on the calcium chloride and moisture. “2.5%KF” “5%KF,” and “7.5%KF” mean the indicated percentages of potassium formate in addition to the 94% calcium chloride. In Table 3, the term NH4F means ammonium formate. TABLE 3 Weight Increase Over Time (grams) Hours Product 16 hrs 20 hrs 24 hrs 40 hrs 77% CaCl2 6.547  8.5854 9.5619 15.3974 94% CaCl2 + 5% NH4F 4.964  6.3635 7.2397 12.9733 94% CaCl2 + 7.5% NH4F 8.2826 10.3386  11.3232  15.2833 94% CaCl2 + 10% NH4F 6.4756 8.0257 9.0649 13.1451

[0012] TABLE 4 Weight Increase Over Time 2 hours 5 hours 24 hours LiCl 0.2913 1.8077 9.8172 KCOOH 0.5877 2.2647 9.993  77% CaCl2 0.0111 0.4246 4.9159 Sm. Mesh CaCl2 0.2023 0.5881 4.9159 Prilled CaCl2 0.0991 0.7136 4.6106

[0013] TABLE 5 Weight Increase Over Time 7 hrs 22 hrs 29 hrs 46 hrs 53 hrs 70 hrs 77% CaCl2 2.7918 10.2764 12.082 15.7432 16.809 19.0542 +2.5% 3.9704 11.7115 13.8077 17.9961 19.2392 21.8174 KCOOH +5.0% 3.8633 11.5287 14.0292 17.9577 19.0072 21.1038 KCOOH +7.5% 4.8065 10.7662 13.1887 16.4462 17.7821 19.7666 KCOOH +10.0% 4.7849 10.0518 12.7825 15.8435 17.2899 18.937 KCOOH

[0014] For Table 5, the indicated percentages of potassium formate were added to the standard 77% calcium chloride, which contained 23% by weight moisture at the beginning of the test. TABLE 6 Weight Increase Over Time 4 hrs 8 hrs 24 hrs 28 hrs 48 hrs 94% CaCl2 + 0.8145 2.1562 8.3738 9.5873 15.6393 10% NaCl 94% CaCl2 + 1.4649 2.6146 8.4068 9.303 14.9175 20% NaCl 100% KCOOH + 2.0998 3.8347 10.8299 12.3011 15.5572 20% NaCl 100% KCOOH + 1.3877 2.6183 9.3758 11.2575 14.1278 20% NaCl 94% CaCl₂ + 0.8164 1.5235 6.7693 7.7308 13.4968 20% CaBr₂

[0015] For Table 6, the indicated additions of sodium chloride and calcium bromide were made to 94% calcium chloride in the case of the first, second and fifth tests, and to a 100% aqueous solution of potassium formate in the third and fourth tests.

[0016] In each case where potassium formate was present, the formation of the drained solution was faster than with compositions not including potassium formate. Potassium formate clearly absorbs more moisture, more readily, than the other salts tested, and clearly enhances these abilities for any of the solution combinations.

[0017] Thus it will be seen that my invention comprises a deliquescent gas drying tablet comprising 0.5% to 100% solid potassium formate and 0% to 99.5% alkali, alkaline earth metal or ammonium formates, chlorides, bromides or mixtures thereof. The composition is preferably comprises about 5% to about 99.5% by weight potassium formate and most preferably about 5% to about 15% potassium formate with the balance being desiccant salts such as alkali (including cesium), alkaline earth metal or ammonium formates, chlorides, bromides or mixtures thereof, with calcium chloride being preferred.

[0018] Following in Table 7 is a comparison of a tablet of the present invention, comprising 77% calcium chloride, 2.5% potassium formate, and water (Tablet Z), to a tablet containing no potassium formate—that is, comprising 77% calcium chloride and water (Tablet A). All four tests were conducted at the same natural gas line site. TABLE 7 Meter pressure 611 612 621 631 Gas flow rate (MMscfd) 1.19 1.183 1.071 0.97 Inlet temperature (° F.) 68 80 90 100 Inlet gas moisture Sat. Sat. Sat. Sat. (lbs H₂O/MMscfd) Outlet gas moisture (lbs H₂O/MMscfd) Tablet A 5.0 5.8 6.4 11.0 Tablet Z 2.9 4.9 5.7 6.1

[0019] Tablet Z, containing 2.5% potassium formate, was not only clearly superior in drying the gas, but also showed no signs of recrystallizing in the sump, in contrast to liquid generated by Tablet A. 

1. A deliquescent gas drying tablet comprising 0.5% to 100% solid potassium formate and 0% to 99.5% alkali, alkaline earth metal or ammonium formates, chlorides, bromides or mixtures thereof.
 2. A deliquescent tablet of claim 1 wherein the potassium formate comprises about 5% to about 99.5% by weight.
 3. A deliquescent tablet of claim 2 comprising about 0.5% to about 95% calcium chloride.
 4. A deliquescent tablet of claim 1 wherein the potassium formate comprises 5% to 95% by weight of said tablet.
 5. A deliquescent tablet of claim 1 wherein the potassium formate comprises 5% to 15% of said tablet.
 6. Method of drying gas comprising contacting gas with a bed of tablets comprising potassium formate thereby forming an aqueous solution of potassium formate comprising water from said gas and potassium formate from said tablet, and separating said solution from said bed of tablets.
 7. Method of claim 6 wherein at least some of said solution is permitted to remain in contact with said bed of tablets and to contact said gas, whereby said solution continues to remove moisture from said gas until said tablets are substantially dissolved.
 8. Method of claim 6 wherein said tablets comprise 5% to 99.5% potassium formate.
 9. Method of claim 8 wherein said tablets comprise about 5% to about 15% potassium formate and the balance is desiccant salts.
 10. Method of claim 6 wherein said gas is natural gas.
 11. Method of claim 9 wherein said balance of desiccant salts comprise predominantly calcium chloride.
 12. Method of claim 6 wherein said separating is accomplished by draining.
 13. Method of claim 7 followed by replacing said bed of tablets with new tablets comprising solid potassium formate.
 14. Method of claim 13 followed by another iteration of the method of claim
 13. 15. Method of claim 9 wherein said desiccant salts include lithium chloride.
 16. Method of claim 9 wherein said desiccant salts include cesium chloride.
 17. Method of claim 6 wherein contacting of said gas with said bed of tablets is accomplished by flowing said gas upwardly through said bed of tablets.
 18. A desiccant tablet comprising about 5% to about 15% by weight potassium formate, about 0.1 to 1% surfactant, and the balance at least one desiccant salt.
 19. A desiccant tablet of claim 18 made by compression, wherein said surfactant is sodium lauryl sulfonate.
 20. A desiccant tablet of claim 18 wherein said at least one desiccant salt comprises calcium chloride.
 21. A deliquescent gas drying tablet comprising 1% to 4% solid potassium formate and 0% to 99% alkali, alkaline earth metal or ammonium formates, chlorides, bromides or mixtures thereof.
 22. A deliquescent tablet of claim 21 wherein the potassium formate comprises about 2% to about 3% by weight.
 23. A deliquescent tablet of claim 22 comprising about 0.5% to about 97% calcium chloride.
 24. Method of drying gas comprising contacting gas with a bed of tablets comprising 1-4% potassium formate by weight thereby forming an aqueous solution comprising water from said gas and potassium formate from said tablet, and separating said solution from said bed of tablets.
 25. Method of claim 24 wherein at least some of said solution is permitted to remain in contact with said bed of tablets and to contact said gas, whereby said solution continues to remove moisture from said gas until said tablets are substantially dissolved.
 26. Method of claim 24 wherein said tablets comprise 2% to 3% potassium formate.
 27. Method of claim 24 wherein said gas is natural gas.
 28. Method of claim 24 wherein said tablets include desiccant salts.
 29. Method of claim 28 wherein said desiccant salts comprise predominantly calcium chloride.
 30. Method of claim 24 wherein said separating is accomplished by draining.
 31. Method of claim 24 followed by replacing said bed of tablets with new tablets comprising solid potassium formate.
 32. Method of claim 31 followed by another iteration of the method of claim
 24. 33. Method of claim 28 wherein said desiccant salts include lithium chloride.
 34. Method of claim 28 wherein said desiccant salts include cesium chloride.
 35. Method of claim 24 wherein contacting of said gas with said bed of tablets is accomplished by flowing said gas upwardly through said bed of tablets.
 36. A desiccant tablet comprising about 1% to about 4% by weight potassium formate, about 0.1 to 1% surfactant, and the balance at least one desiccant salt.
 37. A desiccant tablet of claim 18 made by compression, wherein said surfactant is sodium lauryl sulfonate.
 38. A desiccant tablet of claim 18 wherein said at least one desiccant salt comprises calcium chloride.
 39. A desiccant tablet of claim 36 wherein said potassium formate comprises 2-3% by weight of said tablet. 